Solid phase extraction fundamentals

Poole, C. E, Principles and Practice of Solid-phase Extraction, In Sampling and Sample Preparation for Field and Laboratory Fundamentals and Hew Directions in Sample Preparation, Pawliszyn, J., Ed., Vol. XXXVII, Elsevier Science, Amsterdam, Netherlands, pp. 341-387, 2002. 

After several decades of research, fundamental aspects of the chemical composition and structure of marine organic matter remain elusive. Advances in the chemical characterization of marine organic matter are, in large part, dependent on the development of quantitative methods for its concentration and isolation from seawater. Each of the major methods currently used for the isolation of marine DOM recovers around one-third of the DOM in seawater (solid-phase extractions, using XAD resins or C18 adsorbents, and ultrafiltration). A coupled reverse osmosis-electrodi-alysis method has recently been used to recover an average of 75% 12% of marine DOM from 16 seawater samples however, the method has emerged too recently to have been well tested at this time. 

Another popular and selective extraction technique widely used in bioanalysis is solid phase extraction (SPE). SPE is a separation process utilizing the affinity of the analytes to a solid stationary phase. By manipulating the polarity and pH of the mobile phase, the analytes of interest or undesired impurities pass through stationary phase sequentially according to their physical and chemical properties. For a SPE procedure, a wash step refers to the elution of the unwanted impurities which are discarded and the elution step refers to the elution of the analytes of interest which are collected. While the fundamental remains the same in decades, the continuing invention and introduction of new commercial stationary phases and accessory devices have boosted the application of SPE in bioanalysis and many other fields. 

FIGURE 11.1 A generalized flow scheme that indicates the fundamental elements of LC-MS-based bioanalysis. Abbreviations LLE = liquid-liquid extraction SPE = solid-phase extraction RAM = restricted-access media TEC = turbulent flow liquid chromatography API = atmospheric-pressure ionization APCI = atmospheric-pressure chemical ionization ESI = electrospray ionization SQMS = single-quadrupole mass spectrometry TQMS = triple-quadrupole mass spectrometry TOF = time-of-flight Q-TOF = quadrupole TOF. (Reprinted from Ackermann et al. [4], with permission from John Wiley Sons, Inc.)... 

There are several simple chromatographic calculations that are fundamental to HPLC and to SPE. Solid-phase extraction can be considered to be a simple form of liquid chromatography with a low number of theoretical plates. The sorbent is the stationary phase, and the mobile phase is water or the organic solvent in which the analyte is dissolved. Figure 4.8 shows the separation of two chromatographic peaks, peak 1 and 2. The efficiency of a liquid chromatographic column to separate the two peaks may be expressed by Eq. (4.17) ... 

An understanding of simple methods development is crucial to developing effective environmental applications of solid-phase extraction (SPE). The lour mechanisms outlined in Chapter 2 (reversed phase, normal phase, ion exchange, and mixed mode) are sufficient for the majority of SPE applications in environmental analysis. The molecule s structure and the sample matrix are (he main factors that will determine which mechanism of isolation and separation will be the most appropriate. The fundamental approach to selection of sorbents will be a key topic and many examples are given. This chapter will also discuss applications of SPE to environmental matrices. These include water, soil, and air, for a variety of compounds. 

Before we begin the discussion of specific sample preparation techniques, it is necessary to review some of the fundamental theories that control these separation techniques (see Table 4). Phase equilibrium theories, phase contact, and countercurrent distributions provide the basis for the extraction techniques, e.g., liquid-liquid extractions as well as the various solid-phase extraction techniques. Solubility theories provide the basis for the preparation and dissolution of solid samples. Finally, understanding of the basic physicochemical theories that control intermolecular interactions is critical for successful development of sample preparation methods. 

Phase equilibrium theory is the fundamental basis for many of the separations techniques used for sample preparation, including liquid-liquid extraction, solid-phase extraction, solid-phase microextraction, and HPLC. 

It is fair to say that all metabolic processes are based on, or can be traced back to, chemical processes. By their very nature, however, many of them take place in the liquid or solid phase dictated by the cell structure in which they occur. On the other hand, many of the processes and reactions involve fundamental reactions exchanging gaseous specimens at the outer interface of a cell. An example is our respiration oxygen is extracted from the inhaled air and toxic exchange gases are expelled from the body during exhalation, e.g. one can smell in the breath of a person whether they have been drinking alcohol. 

To understand any extraction technique it is first necessary to discuss some underlying principles that govern all extraction procedures. The chemical properties of the analyte are important to an extraction, as are the properties of the liquid medium in which it is dissolved and the gaseous, liquid, supercritical fluid, or solid extractant used to effect a separation. Of all the relevant solute properties, five chemical properties are fundamental to understanding extraction theory vapor pressure, solubility, molecular weight, hydrophobicity, and acid dissociation. These essential properties determine the transport of chemicals in the human body, the transport of chemicals in the air water-soil environmental compartments, and the transport between immiscible phases during analytical extraction. 

B. Law, S. Weir, and N. A. Ward, Fundamental studies in reversed-phase liquid-solid extraction of basic I ionic interactions, J. Pharm. Biomed. Anal., 70 167 (1992). 

Fundamental studies on the adsorption of supercritical fluids at the gas-solid interface are rarely cited in the supercritical fluid extraction literature. This is most unfortunate since equilibrium shifts induced by gas phase non-ideality in multiphase systems can rarely be totally attributed to solute solubility in the supercritical fluid phase. The partitioning of an adsorbed specie between the interface and gaseous phase can be governed by a complex array of molecular interactions which depend on the relative intensity of the adsorbate-adsorbent interactions, adsorbate-adsorbate association, the sorption of the supercritical fluid at the solid interface, and the solubility of the sorbate in the critical fluid. As we shall demonstrate, competitive adsorption between the sorbate and the supercritical fluid at the gas-solid interface is a significant mechanism which should be considered in the proper design of adsorption/desorption methods which incorporate dense gases as one of the active phases. 

Figure 10 shows a typical measured homodyne waveform and the corresponding numerical fit (solid lines). The measured THz waveform exhibits both the fundamental ECDL difference frequency (Fig. 10(a)) and higher harmonics - predominantly the third harmonic (Fig. 10(b)). Multiple harmonic generation in THz photo-mixers has been previously reported [103], By fitting the observed waveform to a sum of harmonic sinusoidal functions, the amplitude and phase of the THz electric field can be determined separately for the fundamental and third harmonic. The solid line shows a numerical fit to the data. The fundamental extracted frequency, 0.535 THz, compares well to the expected frequency based on the frequency difference of the two ECDL. The extracted E field amplitudes and phases are 3.37 x 10 4 and 2.17 radians for 0.535 THz (Fig. 10(a)) and 5.61 x 10-5 and 3.94 radians for the 1.605 THz third harmonic, respectively (Fig. 10(b)). 

The use of supercritical fluids in separation processes has received considerable attention in the past several years and the fundamentals of supercritical fluid (SCF) extraction and potential applications have been described in a recent review article (p. It is generally known that supercritical conditions enhance the dissolution of solid particles. In comparison with liquid solvents, supercritical fluids have a high diffusivity, a low density and a low viscosity, thus allowing rapid extraction and phase separation. Little information is available in the literature however, on mass transfer coefficients between supercritical fluids and solids. 

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